CN1328164C - Molecular screen ECNU-3 and synthesizing method thereof - Google Patents
Molecular screen ECNU-3 and synthesizing method thereof Download PDFInfo
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- CN1328164C CN1328164C CNB2004100991388A CN200410099138A CN1328164C CN 1328164 C CN1328164 C CN 1328164C CN B2004100991388 A CNB2004100991388 A CN B2004100991388A CN 200410099138 A CN200410099138 A CN 200410099138A CN 1328164 C CN1328164 C CN 1328164C
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Abstract
The present invention relates to a molecular sieve ECNU-3 and a synthesis method thereof, which belong to the fields of inorganic chemical product and the synthesis technology thereof. The molecular sieve takes germanium, boron, oxygen and at least one of silicon, titanium, aluminum, iron and gallium elements as skeleton elements; the molar composition is expressed in an oxide anhydrous form GeO2: xB2O3: ySiO2: zTiO2: phiM2O3, wherein M stands for aluminum, iron and gallium; x is equal to 0 to 0.5; y is equal to 0 to 10; z is equal to 0 to 0.5; phi is equal to 0 to 2. The synthesis method of the molecular sieve comprises the following operation steps: reaction mixture preparation, crystallization and sintering. A new structure of the molecular sieve is manifested by characteristic peaks 2 theta is equal to 7.86 DEG, 10.93 DEG, 20.49 DEG, 21.44 DEG, 22.77 DEG and 26.87 DEG. When the skeleton composition of the molecular sieve is expressed in an oxide anhydrous form GeO2-B2O3-SiO2-TiO2, the molecular sieve is an active component of a catalytic oxidation catalyst for preparing a hydrocarbon oxygen-containing compound; when the skeleton composition of the molecular sieve is expressed in an oxide anhydrous form GeO2-B2O3-SiO2-Al2O3, the molecular sieve is an active component of a solid acid catalyst.
Description
Technical field
The present invention relates to a kind of molecular sieve ECNU-3 and synthetic method thereof, this molecular sieve is a kind of novel texture, is designated the molecular sieve of ECNU-3, belongs to inorganic chemical and synthesis technical field thereof.
Background technology
In general, " zeolite " is the generic term of the crystalline, porous Si-Al molecular sieve of expression.Zeolite structured elementary cell SiO
4And AlO
4Tetrahedron.Yet, since the 1980s, confirmed that above-mentioned zeolite structured peculiar or similar structure also is present in other the oxide compound, as aluminate or phosphate (US 4,310,440), as germanium Si oxide (US 6,077,498).
In addition, International Zeolite Association (International Zeolite Association is called for short " IZA ") is in calendar year 2001 the 13rd international molecular sieve meeting (http: ∥ www.iza-online.org/) zeolite has been carried out further definition.According to the definition of this association, zeolite molecular sieve (zeolite) comprises natural and synthetic zeolite (zeolite), molecular sieve (molecular sieve) and has the zeolite dependency structure and/or the micropore of character characteristics (microporous), mesoporous (mesoporous) material.Thereby term " zeolite molecular sieve " not only can comprise Si-Al molecular sieve, can also comprise the material with the Si-Al molecular sieve structural similitude, as the SiGe molecular sieve.Simultaneously, zeolite molecular sieve is meant that the duct of this material is full of by water molecules and water molecules wherein may be removed the back and its skeleton do not breakdown (US 4,439,409).
Usually, zeolite molecular sieve, its specific structure is to be determined by X-ray diffraction spectrogram (XRD).The different zeolites molecular sieve, its XRD spectra feature difference.Existing synthetic zeolite molecular sieve, (US 2,882 as A type molecular sieve, 243), (US 2 for X type molecular sieve, 882,244), (US 3,130 for Y zeolite, 007), (US 4 for the PHS molecular sieve, 439,409), (US 4,954 for the MCM-22 molecular sieve, 325), all has the XRD spectra feature of characteristics separately.Simultaneously, have identical XRD spectra feature, but the backbone element difference, the performance difference also is different molecular sieve.As, (US 4,410 for the TS-1 molecular sieve, 501) with ZSM-5 molecular sieve (US3,702,886), AlPO-n (n refers to the code name of different structure molecular sieve) molecular sieve (US4,310,440) with SAPO-n (n among n and the AlPO-n is consistent) molecular sieve (US4,440,871), they all have identical XRD spectra feature between the two, but the backbone element difference, the performance difference.Specifically, the TS-1 molecular sieve has the catalyzed oxidation function, and the ZSM-5 molecular sieve has the acid catalysis function; The AlPO-n framework of molecular sieve is electric neutrality, no ion-exchange performance, no catalytic performance, and the SAPO-n framework of molecular sieve is electronegativity, has ion-exchange performance, have the acid catalysis performance.
Summary of the invention
One of purpose of the present invention provides a kind of molecular sieve ECNU-3, it is characterized in that, this molecular sieve is its backbone element with germanium, silicon, oxygen element or with at least a element in germanium, silicon, oxygen element and boron, titanium, aluminium, iron, the gallium element, and its mole composition is expressed as GeO with the anhydrous form of oxide compound
2: xB
2O
3: ySiO
2: zTiO
2: _ M
2O
3, wherein M represents aluminium, iron, gallium, x=0～0.28, and y=1.7～8.7, z=0～0.27, _=0～0.8, its XRD spectra contains the XRD spectral line shown in the table 1,
Table 1
| 2θ/° | d/A° | I/I0×100 |
| 7.06±0.32 7.86±0.24 10.52±0.13 10.93±0.08 16.36±0.25 19.49±0.41 20.49±0.33 21.44±0.23 21.93±0.06 22.77±0.42 26.87±0.32 28.46+0.28 | 12.51±0.06 11.24±0.06 8.40±0.08 8.09±0.05 5.41±0.06 4.55±0.08 4.33±0.05 4.14±0.05 4.05±0.04 3.90±0.02 3.31±0.02 3.13±0.04 | w vs w-m m w w m w-m m m w-m w |
| 29.02±0.22 33.05±0.35 | 3.07±0.04 2.71±0.03 | w w |
*w：＜20；m：20～70；s：70～90；vs：90～100。
Described molecular sieve ECNU-3 is further characterized in that this molecular sieve is its backbone element with germanium, boron, silicon, titanium, oxygen element, and its mole composition is expressed as GeO with the anhydrous form of oxide compound
2: xB
2O
3: ySiO
2: zTiO
2, x=0.11～0.20, y=1.7～6.3, z=0.08～0.27 is that framework of molecular sieve Ti (IV) charateristic avsorption band appears in 210～220nm place at wavelength in its UV-VIS spectrogram, is a kind of catalyst for catalytic oxidation active ingredient for preparing the hydro carbons oxygenatedchemicals.
Described molecular sieve ECNU-3, it is further characterized in that this molecular sieve is its backbone element with germanium, boron, silicon, aluminium, oxygen element, its mole composition is expressed as GeO with the anhydrous form of oxide compound
2: xB
2O
3: ySiO
2: _ Al
2O
3, x=0.11～0.18, y=1.8～6.1, _=0.07～0.8, be 3618cm in wave number in its FTIR spectrogram
-1Framework of molecular sieve Al-OH eigen vibration peak appears in the place, is a kind of solid acid catalysis catalyst activity component.
Two of purpose of the present invention provides the synthetic method of above-mentioned molecular sieve ECNU-3.The technical scheme that realizes this purpose comprises following operation steps: the preparation of reaction mixture, crystallization, roasting.
The synthetic method of a kind of molecular sieve ECNU-3 is characterized in that, operation steps:
The preparation of the first step reaction mixture
GeO in the germanium source in molar ratio
2: the B in the boron source
2O
3: the SiO in the silicon source
2: the TiO in the titanium source
2: the M among the M
2O
3: organic formwork agent: the F-in the fluorine source: H
2O is 1: (0～6): (2～9): (0～0.3 5): (0～1.2): (2.66～13): (0～5): (21～100) preparation feedback mixture, described germanium source is a germanium dioxide, described boron source is boric acid or borate, described silicon source is a silicic acid, silica gel, silicon sol or silicic acid tetraalkyl ester, described titanium source is a tetralkyl titanate, halogenated titanium, titanium oxide, described aluminium source is a sodium metaaluminate, aluminum isopropylate, aluminium hydroxide, the hydrochlorate of activated alumina or aluminium, described source of iron is an iron nitrate, ferric sulfate, iron(ic) chloride, described gallium source is a gallium nitrate, described fluorine source is a Sodium Fluoride, Neutral ammonium fluoride, hydrofluoric acid, silicofluoric acid and silicofluoride, described organic formwork agent is TMBA (Benzyltrimethylammonium, the phenyl trimethylammonium hydroxide), DMHMI (dimethylhexamethyleneimine, dimethyl hexa-methylene amine), DABCO (1,4-diazabicyclo[2.2.2] octane, 1,4-two azo cyclooctane) and TMAD N, N (N, N, N ', N '-tetramethylazodicarboxamide, N, N-tetramethyl-azo acid amides) at least a in, earlier with the germanium source, the boron source is dissolved in the organic formwork agent solution, stir, add the silicon source, the titanium source, the aluminium source, source of iron, the gallium source, the fluorine source, continue to stir, obtain reaction mixture;
The second step crystallization
The reaction mixture that the first step is made is in 130～200 ℃ of hydrothermal crystallizings 5 hours～20 days, after filtration, washing, drying, obtains crystallization product;
The 3rd one-step baking
Second crystallization product that make of step in 400～700 ℃ of roastings 3～40 hours, is obtained products molecule sieve ECNU-3.
Technical scheme of the present invention is further characterized in that, in the first step, and the GeO in the germanium source in molar ratio
2: the B in the boron source
2O
3: the SiO in the silicon source
2: the TiO in the titanium source
2: the M among the M
2O
3: organic formwork agent: the F-in the fluorine source: H
2O is 1: (0.66～6): (2～7): (0.1～0.35): 0: (2.66～13): (0～5): (21～100) preparation feedback mixture; In second step, the reaction mixture that the first step is made was in 150～180 ℃ of hydrothermal crystallizings 3 hours～15 days; In the 3rd step, with second crystallization product that make of step in 500～650 ℃ of roastings 5～20 hours.
The advantage that the present invention has:
1. molecular sieve ECNU-3 of the present invention has complete, novel crystalline structure, Stability Analysis of Structures;
2. the molecular sieve ECNU-3 that obtains of the present invention, the anhydrous form of forming with oxide compound when its main skeleton is expressed as GeO
2-B
2O
3-SiO
2-TiO
2The time, be that framework of molecular sieve Ti (IV) charateristic avsorption band appears in 210～220nm place at wavelength in its UV-VIS spectrogram, be a kind of catalyst for catalytic oxidation active ingredient for preparing the hydro carbons oxygenatedchemicals.
3. the molecular sieve ECNU-3 that obtains of the present invention, the anhydrous form of forming with oxide compound when its main skeleton is expressed as GeO
2-B
2O
3-SiO
2-Al
2O
3The time, be 3618cm in wave number in its FTIR spectrogram
-1Near framework of molecular sieve Al-OH eigen vibration peak appears, be a kind of solid acid catalysis catalyst activity component.
Description of drawings
The XRD spectra of the product of the present invention that Fig. 1 obtains for embodiment 1.XRD determining is to carry out on German Bruker axs type X-ray diffractometer, adopts CuK α.As can be known, compare with the XRD spectra of existing molecular sieve from XRD spectra, it is 2 θ=7.86 °, 10.93 °, 20.49 °, 21.44 °, 22.77 °, 26.87 that the novel texture of this molecular sieve shows as the characteristic peak that has.
Embodiment
All embodiment all operate by the operation steps of technique scheme.
Embodiment 1
The germanium source is a germanium dioxide, and the silicon source is a silica gel, and the boron source is a boric acid, and organic formwork agent is TMBA (Benzyltrimethylammonium).
The preparation of the first step reaction mixture
GeO in the germanium source in molar ratio
2: the B in the boron source
2O
3: the SiO in the silicon source
2: organic formwork agent: H
2O is 1: 0.66: 2: 2.66: 21 preparation feedback mixtures, earlier germanium source, boron source are dissolved in the organic formwork agent solution, and stir, add the silicon source, continue to stir, obtain reaction mixture.
The second step crystallization
The reaction mixture that the first step is made is in 170 ℃ of hydrothermal crystallizings 14 days, after filtration, washing, drying, obtains crystallization product.
The 3rd one-step baking
Second crystallization product that make of step in 550 ℃ of roastings 5 hours, is obtained products molecule sieve ECNU-3.
The anhydrous form that the mole of products molecule sieve ECNU-3 is formed with oxide compound is expressed as GeO
2: 0.12B
2O
3: 1.8SiO
2, x=0.12, y=1.8.
The XRD spectra data of products molecule sieve ECNU-3 are as shown in table 2, meet table 1 data are shown, and XRD spectra as shown in Figure 1.
Table 2
| 2θ/° | d/A° | I/I0×100 |
| 7.06 7.86 | 12.51 11.24 | 10.6 100.0 |
| 10.52 10.93 16.36 19.49 20.49 21.44 21.93 22.77 26.87 28.46 29.02 33.05 | 8.40 8.09 5.41 4.55 4.33 4.14 4.05 3.90 3.31 3.13 3.07 2.71 | 15.9 40.2 5.7 9.6 30.7 11.8 28.0 28.7 13.0 7.2 8.7 6.2 |
*w：＜20；m：20～70；s：70～90；vs：90～100。
Embodiment 2
Implementation process except for the following differences, all the other are all with embodiment 1.
The preparation of the first step reaction mixture
GeO in the germanium source in molar ratio
2: the B in the boron source
2O
3: the SiO in the silicon source
2: organic formwork agent: H
2O is 1: 6: 9: 13: 100 preparation feedback mixtures.
The second step crystallization
In 180 ℃ of hydrothermal crystallizings 5 days.
The anhydrous form that the mole of products molecule sieve ECNU-3 is formed with oxide compound is expressed as GeO
2: 0.28B
2O
3: 8.4SiO
2, x=0.28, y=8.4.
XRD spectra and Fig. 1 of products molecule sieve ECNU-3 are similar.
Embodiment 3～6
Implementation process except for the following differences, all the other are all with embodiment 1.
Embodiment 3
Organic formwork agent is the mixture of TMBA (Benzyltrimethylammonium) and DMHMI (dimethylhexamethyleneimine), and both mol ratios are 1: 1.
Embodiment 4
The boron source is a Sodium Tetraborate, and the silicon source is a silicon sol, and organic formwork agent is DMHMI (dimethylhexamethyleneimine).
Embodiment 5
Organic formwork agent is DABCO (1,4-diazabieyelo[2.2.2] octane).
Embodiment 6
Organic formwork agent is TMAD (N, N, N ', N '-tetramethylazodicarboxamide).
The anhydrous form that the mole of products molecule sieve ECNU-3 is formed with oxide compound is expressed as:
Embodiment 3GeO
2: 0.11B
2O
3: 1.9SiO
2, x=0.11, y=1.9.
XRD spectra and Fig. 1 of products molecule sieve ECNU-3 are similar.
Embodiment 4GeO
2: 0.12B
2O
3: 1.8SiO
2, x=0.12, y=1.8.
XRD spectra and Fig. 1 of products molecule sieve ECNU-3 are similar.
Embodiment 5GeO
2: 0.12B
2O
3: 1.7SiO
2, x=0.12, y=1.7.
XRD spectra and Fig. 1 of products molecule sieve ECNU-3 are similar.
Embodiment 6GeO
2: 0.10B
2O
3: 1.9SiO
2, x=0.10, y=1.9.
XRD spectra and Fig. 1 of products molecule sieve ECNU-3 are similar.
Embodiment 7
Implementation process except for the following differences, all the other are all with embodiment 1.
The fluorine source is a hydrofluoric acid
The preparation of the first step reaction mixture
GeO in the germanium source in molar ratio
2: the B in the boron source
2O
3: the SiO in the silicon source
2: the F-in the fluorine source: organic formwork agent: H
2O is 1: 6: 9: 5: 13: 100 preparation feedback mixtures, earlier germanium source, boron source are dissolved in the organic formwork agent solution, and stir, add the silicon source, continue to stir, add the fluorine source, continue to stir, obtain reaction mixture.
The anhydrous form that the mole of products molecule sieve ECNU-3 is formed with oxide compound is expressed as GeO
2: 0.25B
2O
3: 8.2SiO
2, x=0.25, y=8.2.
XRD spectra and Fig. 1 of products molecule sieve ECNU-3 are similar.
Embodiment 8
Implementation process except for the following differences, all the other are all with embodiment 7.
The fluorine source is a Sodium Fluoride, and organic formwork agent is the mixture of TMBA (Benzyltrimethylammonium) and DABCO (1,4-diazabicyclo[2.2.2] octane), and both mol ratios are 1: 1.
The anhydrous form that the mole of products molecule sieve ECNU-3 is formed with oxide compound is expressed as GeO
2: 0.24B
2O
3: 8.5SiO
2, x=0.27, y=8.5.
XRD spectra and Fig. 1 of products molecule sieve ECNU-3 are similar.
Embodiment 9
Implementation process except for the following differences, all the other are all with embodiment 1.
The titanium source is a tetrabutyl titanate.
The preparation of the first step reaction mixture
GeO in the germanium source in molar ratio
2: the B in the boron source
2O
3: the SiO in the silicon source
2: the TiO in the titanium source
2: organic formwork agent: H
2O is 1: 0.66: 2: 0.1: 2.66: 21 preparation feedback mixture, earlier titanium source, germanium source, boron source are dissolved in the organic formwork agent solution, and stir, add the silicon source, continue to stir, obtain reaction mixture.
The anhydrous form that the mole of products molecule sieve ECNU-3 is formed with oxide compound is expressed as GeO
2: 0.11B
2O
3: 1.7SiO
2: 0.08TiO
2, x=0.11, y=1.7, Z=0.08.
XRD spectra and Fig. 1 of products molecule sieve ECNU-3 are similar.
Embodiment 10
Implementation process except for the following differences, all the other are all with embodiment 7,
The titanium source is a titanium tetrachloride.
The preparation of the first step reaction mixture
GeO in the germanium source in molar ratio
2: the B in the boron source
2O
3: the SiO in the silicon source
2: the TiO in the titanium source
2: the F-in the fluorine source: organic formwork agent: H
2O is 1: 6: 7: 0.35: 5: 13: 100 preparation feedback mixtures: earlier titanium source, germanium source, boron source are dissolved in the organic formwork agent solution, stir, add the silicon source, continue to stir, add the fluorine source, continue to stir, obtain reaction mixture.
The anhydrous form that the mole of products molecule sieve ECNU-3 is formed with oxide compound is expressed as GeO
2: 0.20B
2O
3: 6.3SiO
2: 0.27TiO
2, x=0.20, y=6.3, z=0.27.
XRD spectra and Fig. 1 of products molecule sieve ECNU-3 are similar.
Embodiment 11
Implementation process except for the following differences, all the other are all with embodiment 1.
The aluminium source is a sodium metaaluminate.
The preparation of the first step reaction mixture
GeO in the germanium source in molar ratio
2: the B in the boron source
2O
3: the SiO in the silicon source
2: the Al in the aluminium source
2O
3: organic formwork agent: H
2O is 1: 0.66: 2: 0.2: 2.66: 21 preparation feedback mixture, earlier aluminium source, germanium source, boron source are dissolved in the organic formwork agent solution, and stir, add the silicon source, continue to stir, obtain reaction mixture.
The anhydrous form that the mole of products molecule sieve ECNU-3 is formed with oxide compound is expressed as GeO
2: 0.11B
2O
3: 1.8SiO
2: 0.15Al
2O
3, x=0.11, y=1.8, _=0.15.
XRD spectra and Fig. 1 of products molecule sieve ECNU-3 are similar.
Embodiment 12
Implementation process except for the following differences, all the other are all with embodiment 7.
The aluminium source is an activated alumina.
The preparation of the first step reaction mixture
GeO in the germanium source in molar ratio
2: the B in the boron source
2O
3: the SiO in the silicon source
2: the Al in the aluminium source
2O
3: the F-in the fluorine source: organic formwork agent: H
2O is 1: 6: 7: 1.2: 5: 13: 100 preparation feedback mixtures: earlier aluminium source, germanium source, boron source are dissolved in the organic formwork agent solution, stir, add the silicon source, continue to stir, add the fluorine source, continue to stir, obtain reaction mixture.
The anhydrous form that the mole of products molecule sieve ECNU-3 is formed with oxide compound is expressed as GeO
2: 0.18B
2O
3: 6.1SiO
2: 0.8Al
2O
3, x=0.18, y=6.1, _=0.8.
XRD spectra and Fig. 1 of products molecule sieve ECNU-3 are similar.
Embodiment 13
Implementation process except for the following differences, all the other are all with embodiment 11.
Source of iron is an iron(ic) chloride.
The preparation of the first step reaction mixture
GeO in the germanium source in molar ratio
2: the B in the boron source
2O
3: the SiO in the silicon source
2: the Fe in the source of iron
2O
3: organic formwork agent: H
2O is 1: 0.66: 2: 0.1: 2.66: 21 preparation feedback mixture, earlier germanium source, source of iron, boron source are dissolved in the organic formwork agent solution, and stir, add the silicon source, continue to stir, obtain reaction mixture.
The anhydrous form that the mole of products molecule sieve ECNU-3 is formed with oxide compound is expressed as GeO
2: 0.11B
2O
3: 1.9SiO
2: 0.07Fe
2O
3, x=0.11, y=1.9, _=0.07.
XRD spectra and Fig. 1 of products molecule sieve Al-ECNU-3 are similar.
Embodiment 14
Implementation process except for the following differences, all the other are all with embodiment 7.
The gallium source is a gallium nitrate.
The preparation of the first step reaction mixture
GeO in the germanium source in molar ratio
2: the B in the boron source
2O
3: the SiO in the silicon source
2: the Ga in the gallium source
2O
3: the F-in the fluorine source: organic formwork agent: H
2O is 1: 6: 7: 0.8: 5: 13: 100 preparation feedback mixtures: earlier gallium source, germanium source, boron source are dissolved in the organic formwork agent solution, stir, add the silicon source, continue to stir, add the fluorine source, continue to stir, obtain reaction mixture.
The anhydrous form that the mole of products molecule sieve ECNU-3 is formed with oxide compound is expressed as GeO
2: 0.18B
2O
3: 6.1SiO
2: 0.52Ga
2O
3, x=0.18, y=6.1, _=5.2.
XRD spectra and Fig. 1 of products molecule sieve ECNU-3 are similar.
Embodiment 15
Implementation process except for the following differences, all the other are all with embodiment 1:
The preparation of the first step reaction mixture
GeO in the germanium source in molar ratio
2: the B in the boron source
2O
3: the SiO in the silicon source
2: organic formwork agent: H
2O is 1: 0: 9: 13: 100 preparation feedback mixtures.
The anhydrous form that the mole of products molecule sieve ECNU-3 is formed with oxide compound is expressed as GeO
2: 8.7SiO
2, y=8.7.
XRD spectra and Fig. 1 of products molecule sieve ECNU-3 are similar.
Claims (6)
1. molecular sieve ECNU-3, it is characterized in that, this molecular sieve is its backbone element with germanium, silicon, oxygen element or with at least a element in germanium, silicon, oxygen element and boron, titanium, aluminium, iron, the gallium element, and its mole composition is expressed as GeO with the anhydrous form of oxide compound
2: xB
2O
3: ySiO
2: zTiO
2: _ M
2O
3, wherein M represents aluminium, iron, gallium, x=0～0.28, and y=1.7～8.7, z=0～0.27, _=0～0.8, its XRD spectra contains the XRD spectral line shown in the table 1,
Table 1
*w：＜20；m：20～70；s：70～90；vs：90～100。
2. according to the described molecular sieve ECNU-3 of claim 1, it is characterized in that this molecular sieve is its backbone element with germanium, silicon, oxygen element, its mole composition is expressed as GeO with the anhydrous form of oxide compound
2: ySiO
2, y=1.7～8.7.
3. according to the described molecular sieve ECNU-3 of claim 1, it is characterized in that this molecular sieve is its backbone element with germanium, boron, silicon, titanium, oxygen element, its mole composition is expressed as GeO with the anhydrous form of oxide compound
2: xB
2O
3: ySiO
2: zTiO
2, x=0.11～0.20, y=1.7～6.3, z=0.08～0.27 is that framework of molecular sieve Ti (IV) charateristic avsorption band appears in 210～220nm place at wavelength in its UV-VIS spectrogram, is a kind of catalyst for catalytic oxidation active ingredient for preparing the hydro carbons oxygenatedchemicals.
4. according to the described molecular sieve ECNU-3 of claim 1, it is characterized in that this molecular sieve is its backbone element with germanium, boron, silicon, aluminium, oxygen element, its mole composition is expressed as GeO with the anhydrous form of oxide compound
2: xB
2O
3: ySiO
2: _ Al
2O
3, x=0.11～0.18, y=1.8～6.1, _=0.07～0.8, be 3618cm in wave number in its FTIR spectrogram
-1Framework of molecular sieve Al-OH eigen vibration peak appears in the place, is a kind of solid acid catalysis catalyst activity component.
5. the synthetic method of claim 1,2,3 or 4 described molecular sieve ECNU-3 is characterized in that operation steps:
The preparation of the first step reaction mixture
GeO in the germanium source in molar ratio
2: the B in the boron source
2O
3: the SiO in the silicon source
2: the TiO in the titanium source
2: the M among the M
2O
3: organic formwork agent: the F in the fluorine source
-: H
2O is 1: (0～6): (2～9): (0～0.35): (0～1.2): (2.66～13): (0～5): (21～100) preparation feedback mixture, described germanium source is a germanium dioxide, described boron source is boric acid or borate, described silicon source is a silicic acid, silica gel, silicon sol or silicic acid tetraalkyl ester, described titanium source is a tetralkyl titanate, halogenated titanium, titanium oxide, described aluminium source is a sodium metaaluminate, aluminum isopropylate, aluminium hydroxide, the hydrochlorate of activated alumina or aluminium, described source of iron is an iron nitrate, ferric sulfate, iron(ic) chloride, described gallium source is a gallium nitrate, described fluorine source is a Sodium Fluoride, Neutral ammonium fluoride, hydrofluoric acid, silicofluoric acid and silicofluoride, described organic formwork agent is the phenyl trimethylammonium hydroxide, dimethyl hexa-methylene amine, 1,4-two azo cyclooctane and N, at least a in the N-tetramethyl-azo acid amides, earlier with the germanium source, the boron source is dissolved in the organic formwork agent solution, stir, add the silicon source, the titanium source, the aluminium source, source of iron, the gallium source, the fluorine source, continue to stir, obtain reaction mixture;
The second step crystallization
The reaction mixture that the first step is made is in 130～200 ℃ of hydrothermal crystallizings 5 hours～20 days, after filtration, washing, drying, obtains crystallization product;
The 3rd one-step baking
Second crystallization product that make of step in 400～700 ℃ of roastings 3～40 hours, is obtained products molecule sieve ECNU-3.
6. the synthetic method of the described molecular sieve ECNU-3 of claim 4 is characterized in that, in the first step, and the GeO in the germanium source in molar ratio
2: the B in the boron source
2O
3: the SiO in the silicon source
2: the TiO in the titanium source
2: the M among the M
2O
3: organic formwork agent: the F in the fluorine source
-: H
2O is 1: (0.66～6): (2～7): (0.1～0.35): 0: (2.66～13): (0～5): (21～100) preparation feedback mixture; In second step, the reaction mixture that the first step is made was in 150～180 ℃ of hydrothermal crystallizings 3 hours～15 days; In the 3rd step, with second crystallization product that make of step in 500～650 ℃ of roastings 5～20 hours.
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| CN106587096B (en) * | 2016-12-22 | 2018-12-21 | 中国科学院山西煤炭化学研究所 | A kind of hydrogen type molecular sieve and preparation method thereof and the application in preparing propylene from methanol |
| CN106865567B (en) * | 2017-01-13 | 2018-02-23 | 华东师范大学 | A kind of molecular sieves of ECNU 16 and its preparation and application |
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